CN105121494B - Photosensitive epoxy composition and optical waveguide core layer formation curability film and used their fiber waveguide, optical electrical transmission use hybrid flexible print wiring board - Google Patents

Photosensitive epoxy composition and optical waveguide core layer formation curability film and used their fiber waveguide, optical electrical transmission use hybrid flexible print wiring board Download PDF

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Publication number
CN105121494B
CN105121494B CN201480022025.XA CN201480022025A CN105121494B CN 105121494 B CN105121494 B CN 105121494B CN 201480022025 A CN201480022025 A CN 201480022025A CN 105121494 B CN105121494 B CN 105121494B
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epoxy resin
fiber waveguide
composition
sandwich layer
photosensitive
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CN105121494A (en
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平山智之
田中直幸
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Nitto Denko Corp
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Nitto Denko Corp
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/045—Light guides
    • G02B1/046—Light guides characterised by the core material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B6/122—Basic optical elements, e.g. light-guiding paths
    • G02B6/1221—Basic optical elements, e.g. light-guiding paths made from organic materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B6/13—Integrated optical circuits characterised by the manufacturing method
    • G02B6/138—Integrated optical circuits characterised by the manufacturing method by using polymerisation
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0385—Macromolecular compounds which are rendered insoluble or differentially wettable using epoxidised novolak resin
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B2006/12035—Materials
    • G02B2006/12069—Organic material
    • G02B2006/12073—Epoxy
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0274—Optical details, e.g. printed circuits comprising integral optical means
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0393—Flexible materials

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optical Integrated Circuits (AREA)
  • Materials For Photolithography (AREA)
  • Epoxy Resins (AREA)

Abstract

The present invention is a kind of photosensitive epoxy composition, and it contains：Cresol novolak type polyfunctional epoxy resin (A), there is the liquid-state epoxy resin (B) and photoacid generator (C) of fluorene skeleton in main chain, and the mixed weight ratio [(A)/(B)] of above-mentioned (A) and (B) is (A)/(B)=40/60~60/40.Therefore, the photosensitive epoxy composition of the present invention is used as fiber waveguide formation with material, especially as the sandwich layer formation material of fiber waveguide to be formed during sandwich layer, conventional production process need not be changed, the sandwich layer of low-loss and resistance to reflow excellent fiber waveguide can be formed by coating process and roll-to-roll (roll to roll) technique.

Description

Photosensitive epoxy composition and optical waveguide core layer formation curability film, with And used their fiber waveguide, optical electrical transmission to use hybrid flexible print wiring board
Technical field
The present invention relates to be used as being formed in widely used optical electrical in optic communication, optical information processing, other general optics Transmission with the sandwich layer of the fiber waveguide in hybrid flexible print wiring board etc. formation material photosensitive epoxy composition with Optical waveguide core layer formation curability film and photosensitive epoxy composition or optical waveguide core layer formation have been used with solid Change property film and manufacture fiber waveguide, optical electrical transmission use hybrid flexible print wiring board.
Background technology
So far, transmit and used in the optical waveguide core layer formation material with hybrid flexible print wiring board towards optical electrical The photosensitive polymer combination of liquid, carries out ultraviolet (UV) across photomask when pattern is formed using the sandwich layer of the material and shines Penetrate, thus make desired core pattern.Although this photosensitive polymer combination photocuring sensitivity is high, after coating From the viewpoint of surface adhesion (adherence), in the roll-to-roll (roll- of the manufacturing process for largely being produced as being conceived to to-roll：R-to-R) as technique during continuous processing, formed when being contacted with roller by above-mentioned photosensitive polymer combination Film can be destroyed, therefore have the shortcomings that R-to-R techniques can not be adapted to, and there is the problem of undercapacity is such (patent document 1)。
Therefore, in order to adapt to continuous processing as R-to-R techniques, usually as photoresist using at normal temperatures In the polymeric material of solid.Now, the molecular weight of polymeric material is higher, then solidifies the flexibility of the amorphous film of last stage More improve, but then, there is the problem of patterning resolution (solidification sensitivity) reduction is such.Conversely, polymeric material Molecular weight it is lower, then patterning resolution is more improved, but flexibility can be reduced.So, the flexibility of usual film and patterning point Resolution is in trade-off relation, there is problem.Thus, in photo-curing property film, it is desirable to take into account it flexible with patterning resolution The optical waveguide core layer formation material of rate, it is proposed that various schemes (patent document 2).
On optical waveguide core layer formation material, according to its use, it is necessary to meet the height of each physical property as solidfied material The multifrequency nature requirement of refractive index, high transparency, high-resolution patterning property, high-fire resistance etc.Therefore, carried out being used to pass through The selections of various raw materials, compounding balance etc. meet the research of each characteristic.
As it was previously stated, in order to which for being conceived to the R-to-R techniques largely produced, optical waveguide core layer formation material generally makes , not only can be by with to forming the method that the uncured thing film that material formed carries out dry film by above-mentioned, but in developing material The requirement of the Technological adaptability as dry film material of low adherence, flexibility in uncured thing etc and cause design of material from It is narrow by spending, and when making dry film, laminate substrate is needed on its two sides, therefore from the viewpoint of resource-saving and cost Also problem can be turned into, therefore still pay attention in developing material the adaptability to wet process, and studied (patent document 3)。
In view of these backgrounds, for example propose by using special phenolic varnish type polyfunctional epoxy resin as host, And then be compounded various resins and meet the photosensitive polymer combination (patent document 4) of above-mentioned characteristic.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2001-281475 publications
Patent document 2：Japanese Unexamined Patent Publication 2011-27903 publications
Patent document 3：Japanese Unexamined Patent Publication 2010-230944 publications
Patent document 4：Japanese Unexamined Patent Publication 2011-237645 publications
The content of the invention
Problems to be solved by the invention
However, being transmitted with the waveguide material of hybrid flexible print wiring board in above-mentioned requirement characteristic, especially towards optical electrical It requires high transparency and in order to be resistant to the resistance to reflow of Reflow Soldering process on production process.
Thus, it is strong it is expected that the R-to-R adaptability for remaining conventional, high-resolution patterning property are turned into, be high transparency and Have the photonasty curable resin composition of resistance to reflow optical waveguide core layer formation material concurrently.
The present invention be in view of such situation and make, its object is to there is provided be used as fiber waveguide formation material, outstanding It is that sandwich layer forms material and has high transparency concurrently, good R-to-R adaptability, high-resolution pattern property and are also equipped with excellent Resistance to reflow photosensitive epoxy composition and optical waveguide core layer formation curability film, use photonasty asphalt mixtures modified by epoxy resin Oil/fat composition or optical waveguide core layer formation curability film and the fiber waveguide that manufactures, optical electrical transmission are electric with hybrid flexible printing Road plate.
The solution used to solve the problem
In order to reach above-mentioned purpose, the 1st purport of the invention is a kind of photosensitive epoxy composition, and it is containing under State (A)~(C) photosensitive epoxy composition, wherein, following (A) and (B) mixed weight ratio [(A)/(B)] for (A)/ (B)=40/60~60/40.
(A) cresol novolak type polyfunctional epoxy resin.
(B) there is the liquid-state epoxy resin of fluorene skeleton in main chain.
(C) photoacid generator.
In addition, the 2nd purport of the present invention is a kind of optical waveguide core layer formation curability film, it is by the above-mentioned 1st master The photosensitive epoxy composition of purport is formed as film-form.
And then, the 3rd purport of the invention is a kind of fiber waveguide, and it is to be formed with base material and covering on the substrate, enter And the fiber waveguide of predetermined pattern and core layer for transmission of optical signals is formed with above-mentioned covering, above-mentioned sandwich layer is by making The photosensitive epoxy composition of above-mentioned 1st purport or the optical waveguide core layer formation of above-mentioned 2nd purport are consolidated with curability film Formed by change.
Also, the 4th purport of the present invention uses hybrid flexible print wiring board for a kind of transmission of optical electrical, and it possesses the above-mentioned 3rd The fiber waveguide of purport.
The present inventor etc. in order to obtain turn into have high transparency concurrently, good R-to-R adaptability, high-resolution patterning property, And possess the photosensitive epoxy composition of the sandwich layer formation material of excellent resistance to reflow fiber waveguide and be repeated Further investigation.Its result is found, is using the photosensitive epoxy group set in the way of as above-mentioned compounding ingredients During compound, it may achieve desired purpose, so as to complete the present invention.
That is, (1) is by using more with the especially fast cresol novolak type of curing rate during photocuring Functional epoxy resins, can be achieved the raising of high-resolution patterning property, the small material of the xanthochromia that (2) are caused by using heating in addition Material and the low material of compounding form and aspect, can be achieved the improvement in terms of resistance to reflow and reduction light loss.And then, (3) R-to-R is adapted to Although property is dependent on the flexibility of the dried film of coating of material at normal temperatures is formed, as described above by normal temperature The cresol novolak type polyfunctional epoxy resin of lower display solid is with showing liquid and having fluorene skeleton in main chain under normal temperature Epoxy resin be compounded with defined Mixing ratio by weight rate, can not hinder other require idiocratically to photonasty asphalt mixtures modified by epoxy resin Oil/fat composition it is uncured when film assign flexibility.Also, (4) on adherence, due to also relying on after coating drying Film liquid parts containing ratio, therefore as described above, pass through the cresol novolak type by solid is shown under normal temperature Polyfunctional epoxy resin is with showing that the epoxy resin with fluorene skeleton is with defined Mixing ratio by weight in liquid and main chain under normal temperature Rate is compounded, and can assign good adherence.Thus, by using photonasty epoxy obtained from being set as above-mentioned formula Resin combination, thus have high transparency concurrently, good R-to-R adaptability, high-resolution patterning property, and obtain excellent resistance to It is reflow, so as to complete the present invention.
The effect of invention
In this way, the present invention is a kind of photosensitive epoxy composition, it contains above-mentioned (A)~(C), and makes above-mentioned (A) Mixed weight ratio [(A)/(B)] with (B) is (A)/(B)=40/60~60/40.Therefore, using the photosensitive epoxy group During sandwich layer of the compound to form such as fiber waveguide, the conventional production process without changing can be by coating process and R-to-R Technique formation low-loss and the sandwich layer of resistance to reflow excellent fiber waveguide.
Also, in the resin component of photosensitive epoxy composition, if setting causes liquid bisphenol A type epoxy resin Containing ratio be below 5 weight %, then can be achieved further reduction adherence in terms of improvement.
Embodiment
Then, embodiments of the present invention are described in detail.But, the present invention is not limited by the embodiment.
《Photosensitive epoxy composition》
The photosensitive epoxy composition of the present invention is using cresol novolak type polyfunctional epoxy resin (A), master There is the liquid-state epoxy resin of fluorene skeleton (hereinafter sometimes referred to " specific liquid-state epoxy resin " in chain.) (B) and photoacid generator (C) obtained from.It should be noted that in the present invention, " liquid ", " solid " are referred respectively at a temperature of normal temperature (25 DEG C) " liquid " state of presentation (presentation mobility), " solid " state.
Hereinafter, the various composition headed by above-mentioned (A)~(C) is illustrated successively.
<Cresol novolak type polyfunctional epoxy resin (A)>
General above-mentioned cresol novolak type polyfunctional epoxy resin (A) is at normal temperatures solid, for example, can include down State the cresol novolak type epoxy resin represented by formula (1).
(in above-mentioned formula (1), R is the alkyl of carbon number 1~6, be can be the same or different each other.In addition, n is positive number.〕
In above-mentioned formula (1), all methyl of preferably R.Specifically, can include YDCN-704A, YDCN-700-10, YDCN-700-7, YDCN-700-5 (being Nippon Steel ＆ Sumitomo Metal Corporation's system) etc..These can be used alone or group Two or more is closed to use.
<Specific liquid-state epoxy resin (B)>
Above-mentioned specific liquid-state epoxy resin (B) is the liquid-state epoxy resin with fluorene skeleton in main chain, is at normal temperatures Liquid, for example, can include the epoxy resin represented by following formulas (2).
(in formula (2), R1~R4For hydrogen atom or the alkyl of carbon number 1~6, it can be the same or different.In addition, R5And R6 For hydrogen atom or methyl, it can be the same or different.N represents 0~10 integer independently of one another.〕
In above-mentioned formula (2), preferably R1~R6For hydrogen atom, specifically, OGSOL EG-200 (Osaka Gas can be included Chemicals Co., Ltd. system).
Also, in the present invention, it is necessary to make above-mentioned cresol novolak type polyfunctional epoxy resin (A) and specific liquid The mixed weight ratio [(A)/(B)] of epoxy resin (B) is (A)/(B)=40/60~60/40.More preferably 45/55~55/45, Particularly preferably 50/50.In above-mentioned mixed weight ratio, when (A) is excessive, photosensitive epoxy composition is formed as into film Shape and during applied to R-to-R techniques, it may appear that the problem of cracking, when (B) is excessive, patterning property when forming sandwich layer pattern It can deteriorate.
Also, in the photosensitive epoxy composition of the present invention, as resin component, except above-mentioned (A) and (B) with Outside, liquid bisphenol A type epoxy resin can also be contained.During containing above-mentioned liquid bisphenol A type epoxy resin, preferably its content is set It is set to the ratio of below the 5 weight % in resin component.More preferably below 3 weight %, more preferably 1 weight % with Under.When the content of above-mentioned liquid bisphenol A type epoxy resin is excessive, the increased tendency of adherence can be observed.Use above-mentioned liquid During bisphenol A type epoxy resin, as described above, it is preferred to it is set as the ratio below 5 weight %, can be appropriate according to its occupation mode Selection is preferably in the way of below 5 weight % ratio uses liquid bisphenol A type epoxy resin or without using liquid bisphenol A The mode [i.e., resin component only includes the mode of above-mentioned (A) and (B)] of type epoxy resin.
<Photoacid generator (C)>
Above-mentioned photoacid generator (C) assigns the curability based on light irradiation to photosensitive epoxy composition, therefore for example Used to assign ultra-violet solidified.
As above-mentioned photoacid generator (C), for example, it can include benzoin class, benzoin alkyl ethers, acetophenones, amino Photoacid generator (the light of acetophenones, Anthraquinones, thioxanthene ketone class, ketal class, benzophenone, xanthone, phosphinoxides etc. Cationic curing initiator).Specifically, the lithium antimonic salt of triphenylsulfonium, 2,2- dimethoxy -1,2- hexichol can be included Base ethane -1- ketone, 1- hydroxy-cyclohexyl-phenyls -one, 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone, 1- (4- (2- hydroxyls Ethyoxyl)-phenyl) -2- hydroxy-2-methyl -1- propane, 2- hydroxyls -1- { 4- (4- (2- hydroxy-2-methyls-propiono)-benzyls Base) phenyl -2- methyl-propan -1- ketone, 2- benzyl -2- dimethylaminos -1- (4- morphlinophenyls)-butanone -1,2- methyl - 1- (4- methylthiophenyis) -2- morpholino propane -1- ketone, double (2,4,6- trimethylbenzoyls)-phenyl phosphine oxides, 2,4,6- Trimethylbenzoyl-diphenyl-phosphine oxide, double (η 5-2,4- cyclopentadiene -1- bases)-bis- ((1H- pyrroles -1- of 2,6- bis- fluoro- 3 Base)-phenyl) titanium, 2- hydroxyls -1- { 4- (4- (2- hydroxy-2-methyls-propiono)-benzyl) phenyl } -2- methyl-propan -1- ketone Deng.These can be used alone or combine two or more and use.Wherein, seen from as fast curing rate, thick film curability From the point of view of point, the lithium antimonic salt of triphenylsulfonium, 2 are preferably used, 2- dimethoxy -1,2- diphenylethane -1- ketone, 1- hydroxyls - Cyclohexyl-phenyl -one, 2- hydroxyls -1- { 4- (4- (2- hydroxy-2-methyls-propiono)-benzyl) phenyl } -2- methyl-propans - 1- ketone.
On above-mentioned photoacid generator (C) content, relative to the weight of resin component 100 of photosensitive epoxy composition Part, it is preferably set to 0.1~10 parts by weight, particularly preferably more preferably 0.3~3 parts by weight, 0.5~2 parts by weight.That is, light When the content of acid agent (C) is very few, it is difficult to obtain photo-curable satiable, based on light irradiation (ultraviolet irradiation), separately Outside, when the content of photoacid generator (C) is excessive, luminous sensitivity improve, can be observed patterning when cause shape anomaly tendency, with And the tendency for the physical property that the loss after being difficult to be flowed back is required can be observed.
In the photosensitive epoxy composition of the present invention, except above-mentioned cresol novolak type polyfunctional epoxy resin (A), beyond specific liquid-state epoxy resin (B), photoacid generator (C) and then aforementioned liquid bisphenol A type epoxy resin, according to need Will, it can such as include for improving the silane system of cementability or the coupling agent of titanium system, olefin-based oligomer, ENB system Compound, the antioxygens such as the flexibility imparting agent such as the cyclic olefine such as polymer oligomer, polymer, synthetic rubber, organo-silicon compound Agent, defoamer etc..These additives can be suitably compounded in the range of the effect of the present invention is not damaged.These can individually make With or two or more is applied in combination.
The photosensitive epoxy composition of the present invention can be by by above-mentioned cresol novolak type multi-functional epoxy tree Fat (A), specific liquid-state epoxy resin (B), photoacid generator (C) and aforementioned liquid bisphenol A type epoxy resin, as needed Other additives be set to as defined in compounding ratio and stir mixing and prepare.And then, in order to by the present invention photonasty epoxy Resin combination is prepared with coating with the form of varnish, can also under heating (such as 60~90 DEG C or so) stirring and dissolving in having Machine solvent.
As the organic solvent used when preparing above-mentioned coating with varnish, can for example include ethyl lactate, MEK, Cyclohexanone, 2- butanone, DMAC N,N' dimethyl acetamide, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol methyl acetic acid Ester, propylene glycol monomethyl ether, 4-methyl furan, dimethoxy-ethane etc..These organic solvents, which can be used alone or combine, to be made With two or more, it can use to obtain being suitable for the viscosity of coating in right amount.
《Fiber waveguide》
Then, the photosensitive epoxy composition for using the present invention is carried out as the fiber waveguide of the formation material of sandwich layer Explanation.
The fiber waveguide obtained by the present invention is for example constituted comprising following：Base material, formed on the substrate with predetermined pattern Covering (under-clad layer), above-mentioned covering upload optical signals the sandwich layer formed with predetermined pattern so that on above-mentioned sandwich layer The covering (top covering) of formation.Also, the fiber waveguide obtained by the present invention is characterised by that above-mentioned sandwich layer is by foregoing photonasty Composition epoxy resin is formed.In addition, on above-mentioned under-clad layer formation material and top covering formation material, can use comprising phase The covering formation composition epoxy resin of same composition, can also use the composition epoxy resin of different compositions.Need Bright, in the fiber waveguide obtained by the present invention, above-mentioned covering needs to be formed in the refractive index mode smaller than sandwich layer.
Also, the refractive index using the sandwich layer (solidfied material) of the photosensitive epoxy composition formation of the present invention is preferably More than 1.59, it is particularly preferably more than 1.596 refractive index.It should be noted that the refractive index example of above-mentioned sandwich layer (solidfied material) Determined as described below.The sandwich layer (solidfied material) of about 50 μm of thickness is made on the even surface of Silicon Wafer, SAIRON is used TECHNOLOGY CORPORATION prism coupler (Prism Coupler, SPA-4000 model), is determined at 850nm Solidfied material be sandwich layer refractive index.
In the present invention, fiber waveguide for example can be by manufacturing via process as described below.That is, base material is prepared, Coating makes the photosensitive epoxy composition as covering formation material be dissolved in the photosensitive of organic solvent on the base material Property varnish.The photomask for exposing predetermined pattern (fiber waveguide pattern) is configured on the varnish film, across the photomask The light irradiation of ultraviolet etc. is carried out, and then is heated as needed, is thus solidified.Then, it is molten using developer solution Solution removes the unexposed portion of above-mentioned light irradiation, is consequently formed the under-clad layer (section below of covering) of predetermined pattern.
Then, on above-mentioned under-clad layer coating make the photosensitive epoxy composition of the present invention be dissolved in organic solvent and Into sandwich layer formation material (photonasty varnish), be consequently formed the uncured layer of core formation.Now, above-mentioned sandwich layer is coated with to be formed After material (photonasty varnish), heat drying and remove organic solvent, be consequently formed and used for uncured optical waveguide core layer formation Curability film.Then, in core formation with being configured to make what predetermined pattern (fiber waveguide pattern) exposed in uncured aspect Photomask, carries out the light irradiation of ultraviolet etc., and then heated as needed across the photomask.Then, using aobvious The dissolving of shadow liquid removes the unexposed portion of above-mentioned core formation uncured layer, is consequently formed the sandwich layer of predetermined pattern.
Then, coating dissolves the above-mentioned photosensitive epoxy composition as covering formation material on above-mentioned sandwich layer After the photonasty varnish of organic solvent, the light irradiations such as ultraviolet irradiation are carried out, and then carry out as needed at heating Reason, is consequently formed top covering (upper section of covering).By via such process, being capable of the fiber waveguide of manufacturing objective.
As above-mentioned substrate material, such as can include Silicon Wafer, metal substrate, macromolecule membrane, glass substrate. Also, as above-mentioned metal substrate, stainless steel plates such as JIS SUS etc. can be included.In addition, as above-mentioned macromolecule membrane, Specifically, polyethylene terephthalate (PET) film, PEN film, polyamides can be included sub- Amine film etc..Also, its thickness is typically set in the range of 10 μm~3mm.
In above-mentioned light irradiation, ultraviolet irradiation is specifically carried out.It is used as the ultraviolet in the irradiation of above-mentioned ultraviolet Light source, for example, can include low pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp etc..In addition, ultraviolet irradiation amount can generally be enumerated Go out 10~20000mJ/cm2, preferably include 100~15000mJ/cm2, it may be more preferable to include 500~10000mJ/cm2 Left and right.
After the exposure of above-mentioned utilization ultraviolet irradiation, in order that the solidification based on light reaction is completed, can also further it apply Plus heat.It is generally small in 10 seconds~2 at 80~250 DEG C, preferably 100~150 DEG C as above-mentioned heating condition When, be preferably 5 points~1 hour in the range of carry out.
In addition, as above-mentioned covering formation material, such as liquid bisphenol A types epoxy resin, liquid bisphenol F types can be included The various liquid-state epoxy resins such as epoxy resin, liquid hydrogenated bisphenol A type epoxy resin, solid epoxy and then suitably contain The resin combination of foregoing various photoacid generators.And then, material and it is coated with to prepare covering formation in the form of varnish, can be with Known various organic solvents are mixed, to be used in right amount in the way of can obtaining being suitable for the viscosity of coating.
As the organic solvent for above-mentioned varnish preparation, as hereinbefore, for example, ethyl lactate, first and second can be included Ketone, cyclohexanone, 2- butanone, DMAC N,N' dimethyl acetamide, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol methyl Acetic acid esters, propylene glycol monomethyl ether, 4-methyl furan, dimethoxy-ethane etc..These organic solvents can be used alone or group Conjunction uses two or more, to be used in right amount in the way of can obtaining being suitable for the viscosity of coating.
It should be noted that as the coating method of the formation material using each layer on above-mentioned base material, such as can make With following method：Utilize the side of the coating of spin coater, coating machine, circular coating machine (spiral coater), bar coater etc. Method, silk-screen printing, the method injected thereto using sept formation gap and by capillarity utilizes multiple applications machine Method of coating etc. is carried out continuously by roll-to-roll (roll-to-roll) Deng coating machine.In addition, above-mentioned fiber waveguide can also lead to Cross to peel off above-mentioned base material and remove and film-form fiber waveguide is made.
So obtained fiber waveguide for example may be used as fiber waveguide of the optical electrical transmission with hybrid flexible print wiring board.
Embodiment
Then, based on embodiment, the present invention will be described.But, the present invention is not limited to the examples.Need Illustrate, in example, " part ", " % " then refer to weight basis unless otherwise noted.
(embodiment 1)
First, before the fiber waveguide as embodiment is made, prepare as covering formation material and sandwich layer formation material Each photonasty varnish.
<The preparation of covering formation material>
Under dark conditions, by two function of liquid long-chain half aliphatic epoxy resin (EXA-4816, DIC CORPORATION systems) 80 parts, solid multifunctional aliphatic epoxy resin EHPE3150 (Daicel Corporation systems) 20 Part, 2.0 parts of photoacid generator (Adeka Optomer SP-170, ADEKA Corporation systems) are mixed into 40 parts of ethyl lactate In, it is completely dissolved with Hybrid Mixer (KEYENCE societies system, MH500) stirrings under being heated at 85 DEG C, room is subsequently cooled to After warm (25 DEG C), heating pressure filtration is carried out using 1.0 μm of molecular filter of bore dia, is thus prepared as covering formation material Photonasty varnish.
<The preparation of sandwich layer formation material>
Under dark conditions, by the multifunctional aromatic epoxy resin of solid, (YDCN-700-10, Nippon Steel live aurification strain Formula commercial firm system) 60 parts, two functional epoxy resins (OGSOL EG-200, Osaka Gas of the liquid (sticky) containing fluorene skeleton Chemicals Co., Ltd. system) 40 parts, photoacid generator c1 (Adeka Optomer SP-170, ADEKA Corporation System) 1.0 parts be mixed into 40 parts of ethyl lactate, stirring is completely dissolved it under being heated at 85 DEG C, is subsequently cooled to room temperature (25 DEG C) after, heating pressure filtration is carried out using 1.0 μm of molecular filter of bore dia, is thus prepared as the photosensitive of sandwich layer formation material Property varnish.
[making of flexible print wiring board (FPC) integrated type optical waveguide]
<The making of under-clad layer>
Using spin coater, using as the photonasty varnish application of above-mentioned covering formation material 22 μm of total thickness flexible printing On the back side of the circuit board with base material (FPC base materials), organic solvent is dried on hot plate (130 DEG C × 10 minutes), thus The under-clad layer forming layer of its uncured state is formed (it should be noted that by removing base material in this condition, can obtain fiber waveguide Curability film is used in formation).Utilize UV irradiating machines (5000mJ/cm2(I lines filter)) across defined mask pattern (pattern Width/pattern spacing (L/S)=50 μm/200 μm) the uncured under-clad layer forming layer formed is exposed, after progress Heat (130 DEG C × 10 minutes).Then, after (25 DEG C × 3 minutes) water-filling of going forward side by side of developing in gamma-butyrolacton is washed, on hot plate Make moisture drying (120 DEG C × 10 minutes), thus make under-clad layer (15 μm of thickness).
<The making of sandwich layer>
Coated and formed as sandwich layer after the photonasty varnish of material with spin coater on the under-clad layer formed, on hot plate Organic solvent is dried (130 DEG C × 5 minutes), be consequently formed the uncured core forming layer of uncured filminess.Irradiated with UV Machine (9000mJ/cm2(I lines filter)) across the defined mask pattern (μ of pattern width/pattern spacing (L/S)=50 μm/200 M) the uncured core forming layer formed is exposed, heat (130 DEG C × 10 minutes) after progress.Then, in gamma-butyrolacton Middle development (25 DEG C × 4 minutes) water-filling of going forward side by side is washed, and moisture drying (120 DEG C × 10 minutes) is made on hot plate, regulation is thus made The sandwich layer (50 μm of thickness) of pattern.
<The making of top covering>
The photonasty varnish as above-mentioned covering formation material is coated with spin coater on the sandwich layer formed, forms not solid The top covering forming layer of change state.With UV irradiating machines (5000mJ/cm2(I lines filter)) to the uncured upper bag that is formed Layer forming layer is exposed, and (130 DEG C × 10 minutes) are heated after progress.Then, develop (25 DEG C × 3 points in gamma-butyrolacton Clock) after water-filling of going forward side by side washes, moisture drying (120 DEG C × 10 minutes) is made on hot plate, the top covering (thickness on sandwich layer is thus made 10μm)。
The sandwich layer that so made and under-clad layer is formed with FPC base materials, is formed with the under-clad layer predetermined pattern, enter And fiber waveguide (75 μm of thickness) one-piece type FPC that top covering is formed with the sandwich layer.
(embodiment 2)
In the preparation as the photonasty varnish of sandwich layer formation material, the compounding ratio of resin component is changed into solid many 55 parts of function aromatic epoxy resin (YDCN-700-10, Nippon Steel ＆ Sumitomo Metal Corporation's system), liquid (sticky) bone containing fluorenes 45 parts of two functional epoxy resins (OGSOL EG-200, Osaka Gas Chemicals Co., Ltd. system) of frame.In addition Fiber waveguide is made similarly to Example 1.
(embodiment 3)
In the preparation as the photonasty varnish of sandwich layer formation material, the compounding ratio of resin component is changed into solid many 50 parts of function aromatic epoxy resin (YDCN-700-10, Nippon Steel ＆ Sumitomo Metal Corporation's system), liquid (sticky) bone containing fluorenes 50 parts of two functional epoxy resins (OGSOL EG-200, Osaka Gas Chemicals Co., Ltd. system) of frame.In addition Fiber waveguide is made similarly to Example 1.
(embodiment 4)
In the preparation as the photonasty varnish of sandwich layer formation material, the compounding ratio of resin component is changed into solid many 45 parts of function aromatic epoxy resin (YDCN-700-10, Nippon Steel ＆ Sumitomo Metal Corporation's system), liquid (sticky) bone containing fluorenes 55 parts of two functional epoxy resins (OGSOL EG-200, Osaka Gas Chemicals Co., Ltd. system) of frame.In addition Fiber waveguide is made similarly to Example 1.
(embodiment 5)
In the preparation as the photonasty varnish of sandwich layer formation material, the compounding ratio of resin component is changed into solid Multifunctional 40 parts of aromatic epoxy resin (YDCN-700-10, Nippon Steel ＆ Sumitomo Metal Corporation's system), liquid are (sticky) containing fluorenes 60 parts of two functional epoxy resins (OGSOL EG-200, Osaka Gas Chemicals Co., Ltd. system) of skeleton.Except this with Fiber waveguide is made similarly to Example 1 outside.
(embodiment 6)
In the preparation as the photonasty varnish of sandwich layer formation material, the compounding composition of resin component is replaced with into solid Multifunctional aromatic epoxy resin (YDCN-700-10, Nippon Steel ＆ Sumitomo Metal Corporation's system) 49, liquid are (sticky) containing fluorenes 50 parts of two functional epoxy resins (OGSOL EG-200, Osaka Gas Chemicals Co., Ltd. system) of skeleton, liquid are double 1 part of phenol A types epoxy resin (JER828, Mitsubishi chemical Co., Ltd's system).Make light wave similarly to Example 1 in addition Lead.
(embodiment 7)
In the preparation as the photonasty varnish of sandwich layer formation material, the compounding composition of resin component is replaced with into solid Multifunctional 47 parts of aromatic epoxy resin (YDCN-700-10, Nippon Steel ＆ Sumitomo Metal Corporation's system), liquid are (sticky) containing fluorenes 50 parts of two functional epoxy resins (OGSOL EG-200, Osaka Gas Chemicals Co., Ltd. system) of skeleton, liquid are double 3 parts of phenol A types epoxy resin (JER828, Mitsubishi chemical Co., Ltd's system).Make light wave similarly to Example 1 in addition Lead.
(embodiment 8)
In the preparation as the photonasty varnish of sandwich layer formation material, the compounding composition of resin component is replaced with into solid Multifunctional 45 parts of aromatic epoxy resin (YDCN-700-10, Nippon Steel ＆ Sumitomo Metal Corporation's system), liquid are (sticky) containing fluorenes 50 parts of two functional epoxy resins (OGSOL EG-200, Osaka Gas Chemicals Co., Ltd. system) of skeleton, liquid are double 5 parts of phenol A types epoxy resin (JER828, Mitsubishi chemical Co., Ltd's system).Make light wave similarly to Example 1 in addition Lead.
(comparative example 1)
In the preparation as the photonasty varnish of sandwich layer formation material, the compounding composition of resin component is replaced with only solid 100 parts of the multifunctional aromatic epoxy resin of body (YDCN-700-10, Nippon Steel ＆ Sumitomo Metal Corporation's system).In addition with Embodiment 1 similarly makes fiber waveguide.
(comparative example 2)
In the preparation as the photonasty varnish of sandwich layer formation material, the compounding ratio of resin component is changed into solid many 70 parts of function aromatic epoxy resin (YDCN-700-10, Nippon Steel ＆ Sumitomo Metal Corporation's system), liquid (sticky) bone containing fluorenes 30 parts of two functional epoxy resins (OGSOL EG-200, Osaka Gas Chemicals Co., Ltd. system) of frame.In addition Fiber waveguide is made similarly to Example 1.
(comparative example 3)
In the preparation as the photonasty varnish of sandwich layer formation material, the compounding ratio of resin component is changed into solid many 30 parts of function aromatic epoxy resin (YDCN-700-10, Nippon Steel ＆ Sumitomo Metal Corporation's system), liquid (sticky) bone containing fluorenes 70 parts of two functional epoxy resins (OGSOL EG-200, Osaka Gas Chemicals Co., Ltd. system) of frame.In addition Fiber waveguide is made similarly to Example 1.
(comparative example 4)
In the preparation as the photonasty varnish of sandwich layer formation material, the compounding composition of resin component is replaced with only solid 100 parts of body phenolic varnish type polyfunctional epoxy resin (157S70, Mitsubishi chemical Co., Ltd's system).In addition, photoacid generator is replaced San-Apro Ltd. CPI-200K (photoacid generator c2) is changed to, its consumption is set to 1.0 parts.In addition with embodiment 1 Similarly make fiber waveguide.
Using so obtained photonasty varnish and each fiber waveguide as each sandwich layer formation material, commented for adherence Valency, R-to-R adaptability (crackle) are evaluated, patterning property evaluation (being the related evaluation of sandwich layer formation material) and waveguide are damaged Consumption evaluates (linear impairments) and resistance to reflow evaluation (both be fiber waveguide related evaluation), enters according to following shown methods Row evaluation of measuring.Their result is together shown in 1~table of table 2 described later with compounding composition.
(adherence evaluation)
The photonasty varnish as sandwich layer formation material prepared in above-described embodiment and comparative example is coated with spin coater On thickness 0.8mm Silicon Wafer, (130 DEG C × 5 minutes) are dried on hot plate, uncured film is thus made.Then, (130 DEG C × 10 minutes) are heated after being carried out to obtained uncured film.So obtain the cured film of about 50 μm of thickness.Connect , the surface for confirming above-mentioned cured film is touched using finger, according to its result of following benchmark evaluations.
○：Do not adhere, and do not produce rough surface.
×：There is adhesion, and produce rough surface.
(R-to-R adaptability (crackle) evaluation)
The photonasty varnish as sandwich layer formation material prepared in above-described embodiment and comparative example is coated with spin coater Onto the SUS base materials of 50 μm of thickness, (130 DEG C × 10 minutes) are dried, the uncured film of about 50 μm of thickness is thus made. Core of the uncured film (amorphous film) along diameter 10cm that will be formed on above-mentioned SUS base materials is wound, and is passed through Visually confirm there is flawless generation in film.According to its result of following benchmark evaluations.
○：Do not crack.
×：Crack.
(evaluation of patterning property)
The photonasty varnish as sandwich layer formation material prepared using in above-described embodiment and comparative example, uses optical microphotograph Mirror confirms the sandwich layer pattern formed on the under-clad layer of above-mentioned making.According to its result of following benchmark evaluations.
○：The shape of sandwich layer pattern does not have pattern ripple, hangover, is formed as rectangle.
×：The shape of sandwich layer pattern does not form rectangle, generates the shape anomalies such as pattern ripple or hangover.
(the loss evaluation (linear impairments) of waveguide)
, will be from light source (850nmVCSEL light sources using the fiber waveguide obtained by above-described embodiment and comparative example as sample OP250, three happiness Co. Ltd. systems) vibration light multimode fibre (FFP-G120-0500, three happiness Co. Ltd. system (μ of diameter 50 MMMF, NA=0.2)) light harvesting is carried out, incide in above-mentioned sample.Then, by from the light of sample outgoing with lens (FH14-11, Cleer and peaceful optics makes institute's Co. Ltd. system (multiplying power 20, NA=0.4)) light harvesting is carried out, with light measurement system (Optical Multi Power Meter Q8221, Advantest Corporation systems) evaluate 6 passages.According to its average total losses, according to following Benchmark evaluation linear impairments.
○：Linear loss is below 0.1dB/cm.
×：Linear loss is the result more than 0.1dB/cm.
(resistance to reflow evaluation)
Using the fiber waveguide obtained by above-described embodiment and comparative example as sample, with backflow simulator (SANYOSEIKO Corporation systems, SMT Scope SK-5000) under nitrogen atmosphere exposed to peak temperature 250 DEG C~255 DEG C × 45 seconds In heating process, the evaluation of waveguide loss (linear impairments) is then carried out as described above.According to its knot of following benchmark evaluations Really.
○：Linear loss after being heated at reflux is below 0.1dB/cm.
×：Linear loss after being heated at reflux is the result more than 0.1dB/cm.
[table 1]
(part)
[table 2]
(part)
According to the above results, for cresol novolak type polyfunctional epoxy resin (A) and specific liquid-state epoxy resin (B) mixed weight is than for the photosensitive epoxy composition (embodiment product) in particular range and possessing using above-mentioned sense Photosensitiveness composition epoxy resin formation sandwich layer fiber waveguide for, adherence evaluation, R-to-R adaptability (crackle) evaluate, Good comment is obtained in the evaluation of patterning property, waveguide loss evaluation (linear impairments), whole projects of resistance to reflow evaluation Valency result.
On the other hand, for belonging to cresol novolak type polyfunctional epoxy resin (A) and specific liquid-state epoxy resin (B) mixed weight is than deviate from the photosensitive epoxy composition for being compounded setting of particular range or using only cresols The photosensitive epoxy composition (comparative example product) of phenolic varnish type polyfunctional epoxy resin (A) and possessing is used For the fiber waveguide of the sandwich layer of above-mentioned photosensitive epoxy composition formation, on adherence evaluation, R-to-R adaptability In (crackle) evaluation, the evaluation of patterning property, waveguide loss evaluation (linear impairments), at least one project of resistance to reflow evaluation The evaluation result of difference is obtained.
And then, without using specific liquid-state epoxy resin (B), instead of cresol novolak type polyfunctional epoxy resin (A) it is the multifunctional aromatic epoxy resin of solid (YDCN-700-10, Nippon Steel ＆ Sumitomo Metal Corporation's system), only used In the comparative example 4 of solid novolac type polyfunctional epoxy resin (157S70, Mitsubishi chemical Co., Ltd's system), on made Fiber waveguide waveguide loss evaluation (linear impairments), it is resistance to it is reflow evaluation be difference evaluation result.
The embodiment of the present invention is shown in the above-described embodiments, but above-described embodiment is only to illustrate, and should not Being construed as limiting property is explained.The expectable clear various modifications of those skilled in the art are belonged in the scope of the present invention.
Industrial applicability
The photosensitive epoxy composition of the present invention is partially forming material, especially as core as the composition of fiber waveguide It is useful that layer, which forms material,.Also, using above-mentioned photosensitive epoxy composition make fiber waveguide for example available for light/ Electrical transmission hybrid flexible print wiring board etc..

Claims (8)

1. a kind of photosensitive epoxy composition, it is characterised in that it is the photonasty asphalt mixtures modified by epoxy resin containing following (A)~(C) Oil/fat composition, following (A) and (B) mixed weight are than being that (A)/(B) is (A)/(B)=40/60~60/40, relative to resin The parts by weight of composition 100, the content of following (C) is 0.1~10 parts by weight,
(A) cresol novolak type polyfunctional epoxy resin,
(B) there is the liquid-state epoxy resin of fluorene skeleton in main chain,
(C) photoacid generator.
2. photosensitive epoxy composition according to claim 1, wherein, the resin of photosensitive epoxy composition In composition, also containing liquid bisphenol A type epoxy resin, the containing ratio of the liquid bisphenol A type epoxy resin for 5 weight % with Under.
3. photosensitive epoxy composition according to claim 1, wherein, the multifunctional ring of (A) cresol novolak type Oxygen tree fat is the cresol novolak type epoxy resin represented by following formulas (1),
In above-mentioned formula (1), R is the alkyl of carbon number 1~6, be can be the same or different each other, in addition, n is positive number.
4. photosensitive epoxy composition according to claim 1, wherein, there is the liquid of fluorene skeleton in (B) main chain Epoxy resin is the liquid-state epoxy resin represented by following formulas (2),
In formula (2), R1~R4For hydrogen atom or the alkyl of carbon number 1~6, it can be the same or different, in addition, R5And R6It is former for hydrogen Son or methyl, can be the same or different, n represents 0~10 integer independently of one another.
5. photosensitive epoxy composition according to claim 1, it is the sandwich layer formation material in fiber waveguide, described Fiber waveguide is to be formed with base material and covering on the substrate and then predetermined pattern is formed with the covering and for passing The fiber waveguide of the sandwich layer of optical signals.
6. curability film is used in a kind of optical waveguide core layer formation, it is as the photonasty ring described in any one of Claims 1 to 5 Epoxy resin composition is formed.
7. a kind of fiber waveguide, it is characterised in that it is to be formed with base material and covering on the substrate and then in the covering The fiber waveguide of predetermined pattern and core layer for transmission of optical signals is formed with, above-mentioned sandwich layer is by making claim 1 Optical waveguide core layer formation solidification described in photosensitive epoxy composition or claim 6 described in any one of~5 Formed by property film hardening.
8. hybrid flexible print wiring board is used in a kind of optical electrical transmission, it is characterised in that it possesses the light wave described in claim 7 Lead.
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US20160085151A1 (en) 2016-03-24
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JP2014214179A (en) 2014-11-17

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